EP0222921B1 - Apparatus for preventing pulsating current for liquid chromatography and method therefor - Google Patents

Apparatus for preventing pulsating current for liquid chromatography and method therefor Download PDF

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Publication number
EP0222921B1
EP0222921B1 EP86902914A EP86902914A EP0222921B1 EP 0222921 B1 EP0222921 B1 EP 0222921B1 EP 86902914 A EP86902914 A EP 86902914A EP 86902914 A EP86902914 A EP 86902914A EP 0222921 B1 EP0222921 B1 EP 0222921B1
Authority
EP
European Patent Office
Prior art keywords
liquid
compression chambers
diaphragms
preventing
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP86902914A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0222921A4 (en
EP0222921A1 (en
Inventor
Toshio Tokuda
Tsunemi Tokieda
Norio Ishida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Publication of EP0222921A1 publication Critical patent/EP0222921A1/en
Publication of EP0222921A4 publication Critical patent/EP0222921A4/en
Application granted granted Critical
Publication of EP0222921B1 publication Critical patent/EP0222921B1/en
Expired legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L55/00—Devices or appurtenances for use in, or in connection with, pipes or pipe systems
    • F16L55/04—Devices damping pulsations or vibrations in fluids
    • F16L55/045—Devices damping pulsations or vibrations in fluids specially adapted to prevent or minimise the effects of water hammer
    • F16L55/05—Buffers therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
    • G01N2030/322—Control of physical parameters of the fluid carrier of pressure or speed pulse dampers

Definitions

  • the present invention relates to an apparatus for preventing a pulsating flow in a liquid chromatograph, the apparatus being disposed between a reciprocating plunger and a column of the liquid chromatograph.
  • the invention further relates to a method for preventing a pulsating flow in a liquid chromatograph, wherein a liquid is transferred under a liquid transfer pressure of 5 to 400 bar from a reciprocating plunger used for the liquid chromatograph via an apparatus for preventing pulsating flow to a column used for the liquid chromatograph.
  • a plunger type pump In the most popular method of transferring liquid in the liquid chromatography, a plunger type pump is used and the transfer is performed by a reciprocating motion of the plunger. This generates a pulsating flow of the liquid being transferred, in accordance with the reciprocal motion of the plunger.
  • a conventional control method for eliminating the pulsations in the flow a plurality of plungers are used in such a way that they react with each other to eliminate the pulsations. Nevertheless, this method has not achieved a complete elimination of pulsations in the flow.
  • a method utilizing the elasticity of a spring is not effective in the low pressure range, and is inconvenient in that the rigidity and elasticity of the spring must be adjusted in accordance with changes in the liquid pressure. Further, a method using the combination of a bellows and a spring is effective to a certain extent from a low to a high pressure, but is still inconvenient in that the rigidity of spring must be adjusted.
  • a compression liquid chamber which is used to prevent pulsating flow of a liquid being transferred at a reciprocation cycle of about 1 sec by a piston pump having a maximum capacity of 100 ⁇ l, is composed of a cylindrical portion having an aperture of 80 mm and a height of 88 mm and a conical portion having a depth of 10 mm and located below the cylindrical portion.
  • JP-Y2-57-5570 discloses an apparatus for preventing a pulsating flow in a liquid chromatograph provided between a liquid transfer pump and a column.
  • This known apparatus comprises a liquid transfer pipe consisting of thin walled stainless steel and having an elliptic cross section.
  • a pipe is placed in a pressure vessel, and the gap therebetween is filled with a soft, resilient substance.
  • the pulsation of the liquid causes an elastic deformation of the liquid transfer pipe and also of the resilient substance, and the pulsation is absorbed thereby.
  • such a pipe can only provide a relatively low volume change per unit area and unit pressure and therefore can only prevent pulsating to a very limited degree.
  • there are problems in obtaining a uniform sectional area of the pipe due to the shorter minor axis of its elliptic cross section which increases the amount of liquid held in the apparatus.
  • the object underlying the present invention is to overcome conventional problems as outlined above and to provide an apparatus and a method which are capable of preventing a pulsating flow in a liquid chromatograph in an efficient and reliable manner.
  • this problem is solved in an advantageous manner, wherein the apparatus and the method have an excellent performance for preventing a pulsating flow, a small dead volume, and an excellent operability, evenly throughout the whole region of 5 to 400 bar of ordinary use for the liquid chromatograph.
  • the apparatus according to the present invention is characterized in that a pair of pressure vessels are provided each having an open side and a hollow interior and forming a pair compression chambers in the interior thereof, which are completely filled with a compressible substance wherein the compression chambers are substantially equal in volumes and compressibilities; in that a liquid flow block is disposed between the pressure vessels and has parallel recesses in opposite faces thereof; in that an inlet and an outlet are each connected with both recesses and liquid passages extending from opposite ends of the liquid flow block to the respective recesses; in that a pair of resilient diaphragms are mounted in parallel with each other and in overlying engagement with the respective opposite faces of the liquid flow block on the one hand and in contact with the pressure vessels and the compressible substance in the compression chambers on the other hand, wherein the diaphragms and the recesses define between each other a pair of liquid transfer chambers connected with each other; and in that the total volume of the two compression chambers is 50 to 300 ml, the compressibility of the compressible substance filled
  • the method according to the present invention is characterized in that the liquid is transferred under the provision that a pressure fluctuation is given by the following relation: ⁇ P ⁇ 5,0 + ⁇ (p - 50), wherein 0 ⁇ ⁇ ⁇ 0,1 and P is the liquid transfer pressure which is ensured by using an apparatus for preventing a pulsating flow in the liquid chromatograph, the apparatus being constructed in such a manner that a pair of pressure vessels are provided each having an open side and a hollow interior and forming a pair of compression chambers in the interior thereof, which are completely filled with a compressible substance wherein the compression chambers are substantially equal in volumes and compressibilities; that a liquid flow block is disposed between the pressure vessels and has parallel recesses in opposite faces thereof; that an inlet and an outlet are each connected with both recesses and liquid passages extending from opposite ends of the liquid flow block to the respective recesses; that a pair of resilient diaphragms are mounted in parallel with each other and in overlying engagement with the respective opposite faces of the liquid
  • a liquid transfer pressure P of 50 to 400 bar is used.
  • a volume of the liquid transfer chambers is used which is approximately twice as large as the quantity of liquid being transferred in one stroke.
  • a liquid flow block is used extending from an inlet for liquid being transferred to an outlet for liquid being transferred of the pressure vessels.
  • the ⁇ P/P value expressed in terms of the ratio between the above-mentioned ⁇ P and P is referred to as the flow pulsation ratio and is a principal index value for determining the characteristic for the prevention of pulsating flow.
  • the conventional apparatus for preventing a pulsating flow has a rather large ⁇ P relative to P, and therefore, usually is unable to operate under a pressure exceeding the region of the allowable flow pulsation ratio.
  • the present invention ensures an excellent performance for preventing a pulsating flow throughout the whole region of the liquid transfer pressure from 5 to 400 bar, which is ordinarily used in a liquid chromatograph.
  • the present inventors have established a proper relationship which concretely expresses the performance for the prevention of pulsating flow.
  • the present relationship suggests that, in the region of a relatively lower liquid transfer pressure (P) from 5 to 50 bar, the pressure fluctuation ⁇ P is 5 bar or less and ⁇ P ⁇ P, and that in the region where the liquid transfer pressure (P) exceeds 50 bar, the pressure fluctuation ⁇ P still does not exceed 10% of the liquid transfer pressure.
  • the flow pulsation ratio is determined by the relationship among various terms, such as the dimensions of the apparatus, the volumes of the parts of the apparatus, particularly of the compression chambers and the liquid transfer chamber, the area of the diaphragms, and the elastic property of the elastic substance filled in the compression chambers, etc.
  • the present inventors made intensive research into the relationships among these terms and, as a result, derived the above-mentioned relationship between the liquid transfer pressure P and the pressure fluctuation ⁇ P, this being expressed so as to enable determination of the index value of the flow pulsation ratio in relation to the condition that the total volume of the compression chambers is 50 to 300 ml, the ratio between the total volume of the compression chambers and the total area of the diaphragms is 2 to 5 ml/cm2, and the compressibility of the substance filled in the compression chambers is (30 to 200) x 10 ⁇ 6/bar, as mentioned above.
  • Figure 1 is a sectional view of an apparatus according to the present invention.
  • Figure 1 shows a side view of an apparatus according to the present invention.
  • a liquid flow block 3 is provided with an inlet 7 for liquid being transferred and an outlet 8 for liquid being transferred
  • a liquid transfer chamber 6 is formed by diaphragms 2a and 2b and the liquid flow block 3.
  • Compression chambers 5a and 5b are formed by the diaphragms 2a and 2b and the pressure vessels 1a and 1b.
  • a compressible substance such as silicone rubber, which is a non-fluid rubber elastic body, etc.
  • silicone rubber which is a non-fluid rubber elastic body, etc.
  • a liquid transfer pipe from a plunger type pump is connected to the inlet 7 for liquid being transferred, and a pipe to a separation column is connected to the outlet 8 for liquid being transferred.
  • the diaphragm 2a is arranged parallel with the diaphragm 2b so that pressure is uniformly distributed thereon.
  • the liquid flow block 3 extends over the central portion of the liquid transferring chamber in a direction from the inlet 7 for liquid being transferred to the outlet 8 for liquid being transferred to define the liquid transfer chamber 6 and to minimize dead volume. Flow paths branch out of the inlet 7 for liquid being transferred and the outlet 8 for liquid being transferred, and communicate with the liquid transfer chamber 6.
  • a plunger used for the liquid chromatograph ordinarily transfers about 100 ⁇ l of liquid in one stroke, at a maximum.
  • a maximum of 100 ⁇ l of liquid is transferred in the first one second, and no liquid is transferred in the next one second.
  • This cycle is continuously repeated.
  • a pulsating flow at an interval of one second is generated in this case.
  • the diaphragms 2a and 2b are pressed toward the compression chambers 5a and 5b, respectively, the non-fluid rubber elastic body filled in the compression chambers is compressed, and the pressure rise is alleviated.
  • the compressed non-fluid rubber elastic body pushed back the diaphragms 2a and 2b to transfer liquid with the resulting alleviated pressure drop.
  • the plunger pump used for the liquid chromatograph usually transfers a maximum of about 100 ⁇ l of liquid during a plunger transferring stroke
  • the pulsating flow can be prevented or mitigated if about 50 ⁇ l, a quantity equivalent to about a half of the maximum flow, can be absorbed by compression of the compression chambers, restraining a pressure rise to the smallest possible value, during the plunger transferring stroke.
  • the volume of the compression chambers are as large as possible
  • the compression chambers are filled with a compressible substance having as high a compressibility as possible, and diaphragms having an area and an elastic limit as large as possible are used.
  • the compression chambers preferably have a volume of 50 to 300 ml, more preferably within a range of 100 to 200 ml. If a volume of more than 300 ml is used, the compactness requirement cannot be met, and if a volume of less than 50 ml is used, a sufficient performance cannot be attained because of an insufficient capacity.
  • the compressibility of a compressible substance filled in the compression chambers is sufficient if 50 ⁇ l of liquid can be absorbed at a pressure rise of 5 bar or so, which can be achieved by a compressibility of (30 to 200) x 10 ⁇ 6/bar when the compression chambers have a volume within a range of 50 to 300 ml. Accordingly, an optimum compressibility is preferably selected in accordance with the size of the compression chambers.
  • the diaphragm preferably has an area as large as possible, since deformation is thus minimized, this results in an enlargement of the dimensions of the apparatus for the prevention of pulsating flow, which then cannot meet the compactness requirement and also it becomes difficult technically to seal the compression chambers. If the area of he diaphragms is too small, there is a danger that deformation will be so significant that it will exceed the elastic limit and cause a breakage of the diaphragms. An intensive study was carried out on metal diaphragms made of stainless steel or other materials most preferred in practice, and it was proved that a ratio between the volume of compression chambers and the area of diaphragms has an optimum range of 2 to 5 ml/cm2.
  • a liquid transfer chamber has a volume about twice as large as the quantity of liquid being transferred.
  • the quantity of transferred liquid was 2 ml/min, and the liquid transfer pressure was varied by connecting various columns.
  • a plunger type pump was used to transfer 100 ⁇ l of liquid in one stroke, and the reciprocating motion was repeated 20 times in each trial.
  • the compression chamber had a total volume of 100 ml, the diaphragms had a total area of 30 cm2, and the liquid transfer chamber had a volume of 200 ⁇ l.
  • Table 1 As is obvious from Table 1, an apparatus according to the present invention realizes a reduced flow pulsation ratio evenly over the whole region of the tested liquid transfer pressure, and realizes a pressure fluctuation of 5% or less over the whole region.
  • an apparatus for preventing a pulsating flow in liquid chromatography has an excellent performance as an apparatus sufficiently effective for the prevention of a pulsating flow, and also has the advantages of an excellent operability and small dead volume, because the compression chamber, the diaphragm, and other components have simple shapes.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Reciprocating Pumps (AREA)
  • Pipe Accessories (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
EP86902914A 1985-05-13 1986-05-13 Apparatus for preventing pulsating current for liquid chromatography and method therefor Expired EP0222921B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP99640/85 1985-05-13
JP60099640A JPS61262293A (ja) 1985-05-13 1985-05-13 液体クロマトグラフ用脈流防止装置

Publications (3)

Publication Number Publication Date
EP0222921A1 EP0222921A1 (en) 1987-05-27
EP0222921A4 EP0222921A4 (en) 1988-05-26
EP0222921B1 true EP0222921B1 (en) 1991-10-16

Family

ID=14252654

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86902914A Expired EP0222921B1 (en) 1985-05-13 1986-05-13 Apparatus for preventing pulsating current for liquid chromatography and method therefor

Country Status (5)

Country Link
US (1) US4794954A (enrdf_load_stackoverflow)
EP (1) EP0222921B1 (enrdf_load_stackoverflow)
JP (1) JPS61262293A (enrdf_load_stackoverflow)
DE (1) DE3682022D1 (enrdf_load_stackoverflow)
WO (1) WO1986006815A1 (enrdf_load_stackoverflow)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4016760A1 (de) * 1990-05-25 1991-11-28 Merck Patent Gmbh Chromatographieanlagen
US5183486A (en) * 1990-12-04 1993-02-02 Spectra-Physics, Inc. Apparatus for degassing a liquid
DE19910100A1 (de) * 1999-03-08 2000-09-14 Continental Teves Ag & Co Ohg Schwingungsdämpfungseinrichtung
DE102010027773A1 (de) * 2010-04-15 2011-10-20 Continental Teves Ag & Co. Ohg Pulsationsdämpfungskapsel
CN102430267B (zh) * 2011-09-16 2014-12-10 常州博世伟业生物科技有限公司 一种大流量中低压制备液相色谱稳流装置及其使用方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE540493A (enrdf_load_stackoverflow) * 1955-08-22
GB1464024A (en) * 1974-09-13 1977-02-09 Pye Ltd Pulse dampers for liquid chromatography
JPS575570Y2 (enrdf_load_stackoverflow) * 1978-11-14 1982-02-02
US4222414A (en) * 1979-06-14 1980-09-16 Varian Associates, Inc. Pulse damper for high-pressure liquid chromatography
JPS575570A (en) * 1980-06-13 1982-01-12 Chubu Create Kogyo Kk Power generator
JPS57160060A (en) * 1981-03-28 1982-10-02 Yanagimoto Seisakusho:Kk Pulsating flow preventing device for high speed liquid chromatography
JPS5872795A (ja) * 1981-10-23 1983-04-30 日産自動車株式会社 燃料配管の圧力脈動除去装置
US4427029A (en) * 1982-11-12 1984-01-24 Scientific Systems, Inc. Pulse damper for chromoatography systems
DE3306631C1 (de) * 1983-02-25 1984-07-19 Hewlett-Packard GmbH, 7030 Böblingen Hochdruckfluessigkeitsdaempfer
US4552182A (en) * 1983-04-21 1985-11-12 Varian Associates, Inc. Hydraulic pulse dampener employing two stiff diaphragms and nesting members
US4548713A (en) * 1984-03-02 1985-10-22 The Perkin-Elmer Corporation Pulse damper
US4629562A (en) * 1985-08-06 1986-12-16 Scientific Systems, Inc. Pulse dampener

Also Published As

Publication number Publication date
US4794954A (en) 1989-01-03
DE3682022D1 (de) 1991-11-21
JPS61262293A (ja) 1986-11-20
WO1986006815A1 (en) 1986-11-20
JPH0335555B2 (enrdf_load_stackoverflow) 1991-05-28
EP0222921A4 (en) 1988-05-26
EP0222921A1 (en) 1987-05-27

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